US2708203A - Preparation of polymeric titanium organic compounds - Google Patents
Preparation of polymeric titanium organic compounds Download PDFInfo
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- US2708203A US2708203A US337438A US33743853A US2708203A US 2708203 A US2708203 A US 2708203A US 337438 A US337438 A US 337438A US 33743853 A US33743853 A US 33743853A US 2708203 A US2708203 A US 2708203A
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- Prior art keywords
- polymeric
- titanium
- acylate
- reaction
- product
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- 239000010936 titanium Substances 0.000 title description 33
- 229910052719 titanium Inorganic materials 0.000 title description 32
- -1 titanium organic compounds Chemical class 0.000 title description 15
- 238000002360 preparation method Methods 0.000 title description 2
- ODIGIKRIUKFKHP-UHFFFAOYSA-N (n-propan-2-yloxycarbonylanilino) acetate Chemical compound CC(C)OC(=O)N(OC(C)=O)C1=CC=CC=C1 ODIGIKRIUKFKHP-UHFFFAOYSA-N 0.000 claims description 31
- 238000000034 method Methods 0.000 claims description 12
- RTAQQCXQSZGOHL-UHFFFAOYSA-N Titanium Chemical compound [Ti] RTAQQCXQSZGOHL-UHFFFAOYSA-N 0.000 description 29
- 239000000047 product Substances 0.000 description 24
- 238000006243 chemical reaction Methods 0.000 description 21
- 150000001732 carboxylic acid derivatives Chemical class 0.000 description 16
- 239000002253 acid Substances 0.000 description 12
- 238000009835 boiling Methods 0.000 description 12
- 238000004821 distillation Methods 0.000 description 11
- FERIUCNNQQJTOY-UHFFFAOYSA-N Butyric acid Chemical compound CCCC(O)=O FERIUCNNQQJTOY-UHFFFAOYSA-N 0.000 description 10
- 125000000217 alkyl group Chemical group 0.000 description 6
- 238000004519 manufacturing process Methods 0.000 description 6
- 229910052751 metal Inorganic materials 0.000 description 6
- 239000002184 metal Substances 0.000 description 6
- 239000000376 reactant Substances 0.000 description 6
- QCWXUUIWCKQGHC-UHFFFAOYSA-N Zirconium Chemical compound [Zr] QCWXUUIWCKQGHC-UHFFFAOYSA-N 0.000 description 5
- 150000007513 acids Chemical class 0.000 description 5
- ZRHOFLXFAAEXEE-UHFFFAOYSA-J butanoate;titanium(4+) Chemical compound [Ti+4].CCCC([O-])=O.CCCC([O-])=O.CCCC([O-])=O.CCCC([O-])=O ZRHOFLXFAAEXEE-UHFFFAOYSA-J 0.000 description 5
- 150000001735 carboxylic acids Chemical class 0.000 description 5
- 229910052726 zirconium Inorganic materials 0.000 description 5
- 239000007795 chemical reaction product Substances 0.000 description 4
- 239000000203 mixture Substances 0.000 description 4
- ZQPPMHVWECSIRJ-KTKRTIGZSA-N oleic acid Chemical compound CCCCCCCC\C=C/CCCCCCCC(O)=O ZQPPMHVWECSIRJ-KTKRTIGZSA-N 0.000 description 4
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 4
- WRIDQFICGBMAFQ-UHFFFAOYSA-N (E)-8-Octadecenoic acid Natural products CCCCCCCCCC=CCCCCCCC(O)=O WRIDQFICGBMAFQ-UHFFFAOYSA-N 0.000 description 3
- WGOMEMWEJIKLSU-UJUIXPSJSA-J (z)-octadec-9-enoate;titanium(4+) Chemical compound [Ti+4].CCCCCCCC\C=C/CCCCCCCC([O-])=O.CCCCCCCC\C=C/CCCCCCCC([O-])=O.CCCCCCCC\C=C/CCCCCCCC([O-])=O.CCCCCCCC\C=C/CCCCCCCC([O-])=O WGOMEMWEJIKLSU-UJUIXPSJSA-J 0.000 description 3
- LQJBNNIYVWPHFW-UHFFFAOYSA-N 20:1omega9c fatty acid Natural products CCCCCCCCCCC=CCCCCCCCC(O)=O LQJBNNIYVWPHFW-UHFFFAOYSA-N 0.000 description 3
- QSBYPNXLFMSGKH-UHFFFAOYSA-N 9-Heptadecensaeure Natural products CCCCCCCC=CCCCCCCCC(O)=O QSBYPNXLFMSGKH-UHFFFAOYSA-N 0.000 description 3
- ZQPPMHVWECSIRJ-UHFFFAOYSA-N Oleic acid Natural products CCCCCCCCC=CCCCCCCCC(O)=O ZQPPMHVWECSIRJ-UHFFFAOYSA-N 0.000 description 3
- 239000005642 Oleic acid Substances 0.000 description 3
- 235000021355 Stearic acid Nutrition 0.000 description 3
- 238000005917 acylation reaction Methods 0.000 description 3
- 150000001336 alkenes Chemical class 0.000 description 3
- 125000004429 atom Chemical group 0.000 description 3
- 125000004432 carbon atom Chemical group C* 0.000 description 3
- 125000000753 cycloalkyl group Chemical group 0.000 description 3
- QXJSBBXBKPUZAA-UHFFFAOYSA-N isooleic acid Natural products CCCCCCCC=CCCCCCCCCC(O)=O QXJSBBXBKPUZAA-UHFFFAOYSA-N 0.000 description 3
- QIQXTHQIDYTFRH-UHFFFAOYSA-N octadecanoic acid Chemical compound CCCCCCCCCCCCCCCCCC(O)=O QIQXTHQIDYTFRH-UHFFFAOYSA-N 0.000 description 3
- OQCDKBAXFALNLD-UHFFFAOYSA-N octadecanoic acid Natural products CCCCCCCC(C)CCCCCCCCC(O)=O OQCDKBAXFALNLD-UHFFFAOYSA-N 0.000 description 3
- 239000008117 stearic acid Substances 0.000 description 3
- KFZMGEQAYNKOFK-UHFFFAOYSA-N Isopropanol Chemical compound CC(C)O KFZMGEQAYNKOFK-UHFFFAOYSA-N 0.000 description 2
- BNVBVPNCFXAQEJ-UHFFFAOYSA-J [Ti+4].CCC([O-])=O.CCC([O-])=O.CCC([O-])=O.CCC([O-])=O Chemical compound [Ti+4].CCC([O-])=O.CCC([O-])=O.CCC([O-])=O.CCC([O-])=O BNVBVPNCFXAQEJ-UHFFFAOYSA-J 0.000 description 2
- 230000010933 acylation Effects 0.000 description 2
- 238000013019 agitation Methods 0.000 description 2
- 125000003118 aryl group Chemical group 0.000 description 2
- 150000001875 compounds Chemical class 0.000 description 2
- XBDQKXXYIPTUBI-UHFFFAOYSA-N dimethylselenoniopropionate Natural products CCC(O)=O XBDQKXXYIPTUBI-UHFFFAOYSA-N 0.000 description 2
- 238000010438 heat treatment Methods 0.000 description 2
- 229910052739 hydrogen Inorganic materials 0.000 description 2
- 239000001257 hydrogen Substances 0.000 description 2
- 125000004435 hydrogen atom Chemical class [H]* 0.000 description 2
- KQNPFQTWMSNSAP-UHFFFAOYSA-N isobutyric acid Chemical compound CC(C)C(O)=O KQNPFQTWMSNSAP-UHFFFAOYSA-N 0.000 description 2
- 125000002496 methyl group Chemical group [H]C([H])([H])* 0.000 description 2
- 150000002905 orthoesters Chemical class 0.000 description 2
- 150000003254 radicals Chemical class 0.000 description 2
- JMXKSZRRTHPKDL-UHFFFAOYSA-N titanium ethoxide Chemical compound [Ti+4].CC[O-].CC[O-].CC[O-].CC[O-] JMXKSZRRTHPKDL-UHFFFAOYSA-N 0.000 description 2
- VXUYXOFXAQZZMF-UHFFFAOYSA-N titanium(IV) isopropoxide Chemical compound CC(C)O[Ti](OC(C)C)(OC(C)C)OC(C)C VXUYXOFXAQZZMF-UHFFFAOYSA-N 0.000 description 2
- ZOAMZFNAPHWBEN-UHFFFAOYSA-N 2-$l^{1}-oxidanylpropane Chemical compound CC(C)[O] ZOAMZFNAPHWBEN-UHFFFAOYSA-N 0.000 description 1
- FYNMXTGXYLXMCP-UHFFFAOYSA-J 2-methylpropanoate zirconium(4+) Chemical compound [Zr+4].CC(C)C([O-])=O.CC(C)C([O-])=O.CC(C)C([O-])=O.CC(C)C([O-])=O FYNMXTGXYLXMCP-UHFFFAOYSA-J 0.000 description 1
- DUFCMRCMPHIFTR-UHFFFAOYSA-N 5-(dimethylsulfamoyl)-2-methylfuran-3-carboxylic acid Chemical compound CN(C)S(=O)(=O)C1=CC(C(O)=O)=C(C)O1 DUFCMRCMPHIFTR-UHFFFAOYSA-N 0.000 description 1
- 125000002252 acyl group Chemical group 0.000 description 1
- 230000006978 adaptation Effects 0.000 description 1
- 150000007933 aliphatic carboxylic acids Chemical class 0.000 description 1
- 125000002877 alkyl aryl group Chemical group 0.000 description 1
- 150000005840 aryl radicals Chemical class 0.000 description 1
- WPYMKLBDIGXBTP-UHFFFAOYSA-N benzoic acid group Chemical group C(C1=CC=CC=C1)(=O)O WPYMKLBDIGXBTP-UHFFFAOYSA-N 0.000 description 1
- 125000000484 butyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])C([H])([H])[H] 0.000 description 1
- 150000007942 carboxylates Chemical class 0.000 description 1
- 238000009833 condensation Methods 0.000 description 1
- 230000005494 condensation Effects 0.000 description 1
- UKMSUNONTOPOIO-UHFFFAOYSA-N docosanoic acid Chemical compound CCCCCCCCCCCCCCCCCCCCCC(O)=O UKMSUNONTOPOIO-UHFFFAOYSA-N 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 150000002148 esters Chemical class 0.000 description 1
- 125000001495 ethyl group Chemical group [H]C([H])([H])C([H])([H])* 0.000 description 1
- 239000003925 fat Substances 0.000 description 1
- 238000001640 fractional crystallisation Methods 0.000 description 1
- 125000003253 isopropoxy group Chemical group [H]C([H])([H])C([H])(O*)C([H])([H])[H] 0.000 description 1
- 239000007788 liquid Substances 0.000 description 1
- 239000000314 lubricant Substances 0.000 description 1
- 239000003879 lubricant additive Substances 0.000 description 1
- 150000002739 metals Chemical class 0.000 description 1
- 238000002156 mixing Methods 0.000 description 1
- 150000002762 monocarboxylic acid derivatives Chemical class 0.000 description 1
- MCCIMQKMMBVWHO-UHFFFAOYSA-N octadecanoic acid;titanium Chemical compound [Ti].CCCCCCCCCCCCCCCCCC(O)=O.CCCCCCCCCCCCCCCCCC(O)=O.CCCCCCCCCCCCCCCCCC(O)=O.CCCCCCCCCCCCCCCCCC(O)=O MCCIMQKMMBVWHO-UHFFFAOYSA-N 0.000 description 1
- WWZKQHOCKIZLMA-UHFFFAOYSA-N octanoic acid Chemical compound CCCCCCCC(O)=O WWZKQHOCKIZLMA-UHFFFAOYSA-N 0.000 description 1
- 239000003921 oil Substances 0.000 description 1
- IPCSVZSSVZVIGE-UHFFFAOYSA-N palmitic acid group Chemical group C(CCCCCCCCCCCCCCC)(=O)O IPCSVZSSVZVIGE-UHFFFAOYSA-N 0.000 description 1
- 229920000642 polymer Polymers 0.000 description 1
- 238000006116 polymerization reaction Methods 0.000 description 1
- 238000001556 precipitation Methods 0.000 description 1
- TVCBSVKTTHLKQC-UHFFFAOYSA-M propanoate;zirconium(4+) Chemical compound [Zr+4].CCC([O-])=O TVCBSVKTTHLKQC-UHFFFAOYSA-M 0.000 description 1
- 235000019260 propionic acid Nutrition 0.000 description 1
- 125000001436 propyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])[H] 0.000 description 1
- IUVKMZGDUIUOCP-BTNSXGMBSA-N quinbolone Chemical compound O([C@H]1CC[C@H]2[C@H]3[C@@H]([C@]4(C=CC(=O)C=C4CC3)C)CC[C@@]21C)C1=CCCC1 IUVKMZGDUIUOCP-BTNSXGMBSA-N 0.000 description 1
- 239000011541 reaction mixture Substances 0.000 description 1
- 238000011084 recovery Methods 0.000 description 1
- 230000001105 regulatory effect Effects 0.000 description 1
- 229920006395 saturated elastomer Polymers 0.000 description 1
- 239000007787 solid Substances 0.000 description 1
- 238000000638 solvent extraction Methods 0.000 description 1
- 125000001424 substituent group Chemical group 0.000 description 1
- 239000004094 surface-active agent Substances 0.000 description 1
- 239000001993 wax Substances 0.000 description 1
Classifications
-
- C—CHEMISTRY; METALLURGY
- C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
- C10M—LUBRICATING COMPOSITIONS; USE OF CHEMICAL SUBSTANCES EITHER ALONE OR AS LUBRICATING INGREDIENTS IN A LUBRICATING COMPOSITION
- C10M1/00—Liquid compositions essentially based on mineral lubricating oils or fatty oils; Their use as lubricants
- C10M1/08—Liquid compositions essentially based on mineral lubricating oils or fatty oils; Their use as lubricants with additives
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07F—ACYCLIC, CARBOCYCLIC OR HETEROCYCLIC COMPOUNDS CONTAINING ELEMENTS OTHER THAN CARBON, HYDROGEN, HALOGEN, OXYGEN, NITROGEN, SULFUR, SELENIUM OR TELLURIUM
- C07F7/00—Compounds containing elements of Groups 4 or 14 of the Periodic Table
- C07F7/003—Compounds containing elements of Groups 4 or 14 of the Periodic Table without C-Metal linkages
-
- C—CHEMISTRY; METALLURGY
- C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
- C10M—LUBRICATING COMPOSITIONS; USE OF CHEMICAL SUBSTANCES EITHER ALONE OR AS LUBRICATING INGREDIENTS IN A LUBRICATING COMPOSITION
- C10M2207/00—Organic non-macromolecular hydrocarbon compounds containing hydrogen, carbon and oxygen as ingredients in lubricant compositions
- C10M2207/10—Carboxylix acids; Neutral salts thereof
- C10M2207/12—Carboxylix acids; Neutral salts thereof having carboxyl groups bound to acyclic or cycloaliphatic carbon atoms
- C10M2207/121—Carboxylix acids; Neutral salts thereof having carboxyl groups bound to acyclic or cycloaliphatic carbon atoms having hydrocarbon chains of seven or less carbon atoms
-
- C—CHEMISTRY; METALLURGY
- C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
- C10M—LUBRICATING COMPOSITIONS; USE OF CHEMICAL SUBSTANCES EITHER ALONE OR AS LUBRICATING INGREDIENTS IN A LUBRICATING COMPOSITION
- C10M2207/00—Organic non-macromolecular hydrocarbon compounds containing hydrogen, carbon and oxygen as ingredients in lubricant compositions
- C10M2207/10—Carboxylix acids; Neutral salts thereof
- C10M2207/12—Carboxylix acids; Neutral salts thereof having carboxyl groups bound to acyclic or cycloaliphatic carbon atoms
- C10M2207/121—Carboxylix acids; Neutral salts thereof having carboxyl groups bound to acyclic or cycloaliphatic carbon atoms having hydrocarbon chains of seven or less carbon atoms
- C10M2207/122—Carboxylix acids; Neutral salts thereof having carboxyl groups bound to acyclic or cycloaliphatic carbon atoms having hydrocarbon chains of seven or less carbon atoms monocarboxylic
-
- C—CHEMISTRY; METALLURGY
- C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
- C10M—LUBRICATING COMPOSITIONS; USE OF CHEMICAL SUBSTANCES EITHER ALONE OR AS LUBRICATING INGREDIENTS IN A LUBRICATING COMPOSITION
- C10M2207/00—Organic non-macromolecular hydrocarbon compounds containing hydrogen, carbon and oxygen as ingredients in lubricant compositions
- C10M2207/10—Carboxylix acids; Neutral salts thereof
- C10M2207/12—Carboxylix acids; Neutral salts thereof having carboxyl groups bound to acyclic or cycloaliphatic carbon atoms
- C10M2207/125—Carboxylix acids; Neutral salts thereof having carboxyl groups bound to acyclic or cycloaliphatic carbon atoms having hydrocarbon chains of eight up to twenty-nine carbon atoms, i.e. fatty acids
-
- C—CHEMISTRY; METALLURGY
- C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
- C10M—LUBRICATING COMPOSITIONS; USE OF CHEMICAL SUBSTANCES EITHER ALONE OR AS LUBRICATING INGREDIENTS IN A LUBRICATING COMPOSITION
- C10M2207/00—Organic non-macromolecular hydrocarbon compounds containing hydrogen, carbon and oxygen as ingredients in lubricant compositions
- C10M2207/10—Carboxylix acids; Neutral salts thereof
- C10M2207/12—Carboxylix acids; Neutral salts thereof having carboxyl groups bound to acyclic or cycloaliphatic carbon atoms
- C10M2207/129—Carboxylix acids; Neutral salts thereof having carboxyl groups bound to acyclic or cycloaliphatic carbon atoms having hydrocarbon chains of thirty or more carbon atoms
-
- C—CHEMISTRY; METALLURGY
- C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
- C10M—LUBRICATING COMPOSITIONS; USE OF CHEMICAL SUBSTANCES EITHER ALONE OR AS LUBRICATING INGREDIENTS IN A LUBRICATING COMPOSITION
- C10M2227/00—Organic non-macromolecular compounds containing atoms of elements not provided for in groups C10M2203/00, C10M2207/00, C10M2211/00, C10M2215/00, C10M2219/00 or C10M2223/00 as ingredients in lubricant compositions
- C10M2227/06—Organic compounds derived from inorganic acids or metal salts
- C10M2227/065—Organic compounds derived from inorganic acids or metal salts derived from Ti or Zr
-
- C—CHEMISTRY; METALLURGY
- C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
- C10N—INDEXING SCHEME ASSOCIATED WITH SUBCLASS C10M RELATING TO LUBRICATING COMPOSITIONS
- C10N2010/00—Metal present as such or in compounds
-
- C—CHEMISTRY; METALLURGY
- C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
- C10N—INDEXING SCHEME ASSOCIATED WITH SUBCLASS C10M RELATING TO LUBRICATING COMPOSITIONS
- C10N2010/00—Metal present as such or in compounds
- C10N2010/08—Groups 4 or 14
-
- C—CHEMISTRY; METALLURGY
- C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
- C10N—INDEXING SCHEME ASSOCIATED WITH SUBCLASS C10M RELATING TO LUBRICATING COMPOSITIONS
- C10N2050/00—Form in which the lubricant is applied to the material being lubricated
- C10N2050/10—Semi-solids; greasy
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- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y10—TECHNICAL SUBJECTS COVERED BY FORMER USPC
- Y10S—TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y10S516/00—Colloid systems and wetting agents; subcombinations thereof; processes of
- Y10S516/01—Wetting, emulsifying, dispersing, or stabilizing agents
- Y10S516/06—Protein or carboxylic compound containing
-
- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y10—TECHNICAL SUBJECTS COVERED BY FORMER USPC
- Y10S—TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y10S516/00—Colloid systems and wetting agents; subcombinations thereof; processes of
- Y10S516/905—Agent composition per se for colloid system making or stabilizing, e.g. foaming, emulsifying, dispersing, or gelling
- Y10S516/917—The agent contains organic compound containing oxygen
- Y10S516/918—The compound contains carboxylic acid ester group
Definitions
- This invention pertains to an acidolysis reaction of polymeric titanium and zirconium acylates, and more particularly to novel and improved processes for manufacturing certain polymeric acylates of said metals, the acylate radicals of which are derived from high-boiling carboxylic acids.
- the direct acylation of ortho esters of titanium by reaction with carboxylic acids causes some condensation and polymerization of the resulting titanium acylate (some times referred to as carboxylate).
- the direct acylation by the methods of U. S. No. 2,621,193 in particular, and to a lesser degree by those of U. S. No. 2,621,195, produces from high-boiling carboxylic acids reaction product mixtures which are diflicult to purify due to the solubility of the acylating acid in the product. Products made from long chain acids, such as, for example, stearic acid, are even more difficult and expensive to purify because solvent extraction must be resorted to for removal of any unreacted acids or oy-products.
- the invention comprises intimately commingling for reaction a polymeric titanium acylate 7 with a carboxylic acid having a higher boiling pointthan the carboxylic acid co-product corresponding to the acyl radicals of the original polymeric titanium acylate, removing the coproduct carboxylic acid formed in the reaction by subjecting the reaction products to distillation, and recovering the polymeric titanium acylate product.
- two moles of a long chain (824 carbon atoms) or high-boiling aliphatic carboxylic acid, such as, for example, stearic acid are suitably commingled and commixed for heating and reaction in a reaction vessel equipped with a distillation head with one mole unit of a polymeric titanium acylate, as for example polymeric titanium propionate having the formula:
- lower boiling acid co-products can be recycled for reuse in the process to make more of the initial polymeric titanium acylate from a titanium ortho ester.
- polymeric titanium acylates of high-boiling car- 'boxylic acids of this invention in addition to their usefulness as waxes, can be employed as surface active agents, lubricants, and lubricant additives, etc. They will vary from viscous liquids to waxy solids, depending upon the chain length or configuration or the acyl groups present therein.
- Example I 176 parts by weight of n-butyric acid was mixed with 284 parts of tetraisopropyl titanate in a distillation type reaction vessel. 1 mole of water was added slowly to the mixture, with good agitation. After the water addition, the temperature of the mixture was raised to 100 C. and 216 parts of isopropanol was distilled ofi and a polymeric titanium butyrate produced which had a few isopropoxy groups (less than /2 mole unit isopropoxy radical per atom of Ti) still remaining attached to the Ti atom. To this polymeric titanium butyrate was added 565 parts of oleic acid with agitation and 186 parts of distillate was then distilled off, of which 164 parts was butyric acid. The reaction product was found to consist essentially of polymeric titanium oleate.
- Example 11 (CH3)2CHCOO -TlO- OCCIHCHDB OZCixHss it was obtained by distilling off the resultant 2 mole parts of isobutyric acid.
- the polymeric or condensed titanium or zirconium acylate useful as a starting reactant herein has substantially the general formula:
- Y and Y in the chain terminating groups comprise an alkyl (methyl, ethyl, propyl, butyl, etc.) or an acyl radical
- R and R equal a radical selected from the group hydrogen, alkyl, cycloalkyl, aryl radical, alkene or an alkylaryl radical
- x is greater than 1 and preferably ranges from 2-100.
- Pr ferably the acylate O O (O&R) and (O i JR) substituent groups are such that in the reaction the exchanged acid evolved or produced therefrom is of relatively low boiling point, e. g., will contain from 2-5 carbon atoms and not more than 8 carbon atoms in its chain.
- polymeric titanium or zirconium acetate polymeric titani um or zirconium propionate, polymeric titanium or zirconium isobutyrate, and the like
- polymeric or condensed titanium acylates are especially useful and preferred for employment. They can be readily prepared by reacting an alkyl orthotitanate, such as tetraethyl titanate, with a carboxylic acid and a regulated quantity of water, as contemplated in my U. S. Patent 2,621,195.
- a mixed titanium acylate hav- 4 ing any desired ratio of acylate groups may be produced.
- Such mixed titanium acylates can be produced by reacting less than the stoichiometric equivalent of carboxylic acid with the titanium acylate and separating the co-product carboxylic acid from the reaction mixture.
- Such a a reaction is represented by the equation:
- the polymer unit being represented by the formula any carboxylic acid boiling higher than n-butyric acid can be used.
- acids include those containing decanoic, hyptylic, sabacic, caprylic, capric, palmitic, oleic, stearic, lauric, behenic, adipic, benzoic, ortho chlorbenzoic, trichloroacetic, etc.
- Mixtures of acids such as, for example, those occurring in natural fats and oils, and the like, are also contemplated for use.
- a wider choice, with regard to boiling point of reactant carboxylic acids, can be used when the co-product carboxylic acid is separated from the product titanium acylate by means other than distillation, as for example fractional crystallization or precipitation of either the coproduct carboxylic acid or the product polymeric titanium acylate.
- a process for acidolysis of a polymeric group IV metal acylate corresponding to the formula wherein Y and Y are selected from the group consisting of an alkyl and acyl radical, R and R are selected from the group consisting of hydrogen, alkyl, cycloalkyl, aryl, alkene and alkylaryl, and x is a number greater than 1, with a carboxylic acid having a higher boiling point than the carboxylic acid co-product which corresponds to the acyl radical of said polymeric metal acylate reactant, removing by distillation from the reaction mass co-product carboxylic acid formed in the reaction, and recovering the resulting polymeric group IV metal acylate product.
- a process for producing a polymeric titanium acylate comprising reacting about one mole unit of a polymeric titanium acylate corresponding to the formula:
- R and R are selected from the group consist ing of an alkyl, cycloalkyl, aryl, alkene and alkylaryl radical, and x is a number greater than 1 with about two moles of a saturated, monocarbcxylic acid having a higher boiling point than the carboxylic acid product of an acyl radical in said acylate reactant, removing by distillation co-product acid formed in the reaction, and recovering the desired polymeric titanium acylate reaction product.
- a process for the production of polymeric titanium stearate by commingling and reacting in a reaction vessel about two moles parts of stearic acid with one mole part of polymeric titanium butyrate, removing by distillation co-product butyric acid formed in the reaction and recovering the resulting acylate product.
- a process for the production of polymeric titanium oleate by commingling and reacting in a reaction vessel about two moles parts of oleic acid with one mole party of polymeric titanium butyrate, removing by distillation co-product butyric acid formed in the reaction and recovering the resulting acylate product.
- a process for the production of polymeric titanium oleate by commingling and reacting in a reaction vessel about two moles parts of oleic acid with one mole part of polymeric titanium propionate, removing by distillation co-product propionic acid formed in the reaction and recovering the resulting acylate product.
- a process for producing polymeric mixed titanium acylates comprising commingling and reacting a polymeric titanium acylate corresponding to the formula:
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- Oil, Petroleum & Natural Gas (AREA)
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- Chemical Kinetics & Catalysis (AREA)
- General Chemical & Material Sciences (AREA)
- Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
Description
Unite PREPARATEON 0F PGLYMERIC TITANIUNE GRGANIC COMPOUNDS John H. Haslam, Wilmington, DeL, assignor to E. I. du Pont de Nernours and Company, Wilmington, Del. a corporation of Delaware No Drawing. Application February 17, 1953, Serial No. 337,438
7 Claims. (Cl. 260-414) This invention pertains to an acidolysis reaction of polymeric titanium and zirconium acylates, and more particularly to novel and improved processes for manufacturing certain polymeric acylates of said metals, the acylate radicals of which are derived from high-boiling carboxylic acids.
The direct acylation of ortho esters of titanium by reaction with carboxylic acids causes some condensation and polymerization of the resulting titanium acylate (some times referred to as carboxylate). The direct acylation, by the methods of U. S. No. 2,621,193 in particular, and to a lesser degree by those of U. S. No. 2,621,195, produces from high-boiling carboxylic acids reaction product mixtures which are diflicult to purify due to the solubility of the acylating acid in the product. Products made from long chain acids, such as, for example, stearic acid, are even more difficult and expensive to purify because solvent extraction must be resorted to for removal of any unreacted acids or oy-products.
It is among the objects of this invention to overcome these and other disadvantages in polymeric Group IV metal acylate manufacture, and to provide, in particular, a new acyl radical exchange reaction of polymeric titanium and zirconium acylates. A further object 'is to provide an improved, direct process for the manufacture of organic solvent-soluble, relatively pure polymeric acylates of titanium and zirconium of relatively high-boiling carboxylic acids. Other objects will be apparent from the ensuing description.
These objects are accomplished herein by mixing and reacting a polymeric group IV metal acylate with a carboxylic acid and separating the acylate product from the co-product carboxylic acid formed from the exchanged acyl radical of the initial polymeric acylate.
More specifically, the invention comprises intimately commingling for reaction a polymeric titanium acylate 7 with a carboxylic acid having a higher boiling pointthan the carboxylic acid co-product corresponding to the acyl radicals of the original polymeric titanium acylate, removing the coproduct carboxylic acid formed in the reaction by subjecting the reaction products to distillation, and recovering the polymeric titanium acylate product.
In one preferred adaptation of the invention, two moles of a long chain (824 carbon atoms) or high-boiling aliphatic carboxylic acid, such as, for example, stearic acid, are suitably commingled and commixed for heating and reaction in a reaction vessel equipped with a distillation head with one mole unit of a polymeric titanium acylate, as for example polymeric titanium propionate having the formula:
0 (i) l C 2H5] TiO- I 11.02000 OCCaHt mula:
i O (J) 0 H351 if desired, lower boiling acid co-products can be recycled for reuse in the process to make more of the initial polymeric titanium acylate from a titanium ortho ester.
The polymeric titanium acylates of high-boiling car- 'boxylic acids of this invention, in addition to their usefulness as waxes, can be employed as surface active agents, lubricants, and lubricant additives, etc. They will vary from viscous liquids to waxy solids, depending upon the chain length or configuration or the acyl groups present therein.
To a clearer understanding of the invention, the following examples are given. These are merely in illustration and not in limitation of the invention.
Example I 176 parts by weight of n-butyric acid was mixed with 284 parts of tetraisopropyl titanate in a distillation type reaction vessel. 1 mole of water was added slowly to the mixture, with good agitation. After the water addition, the temperature of the mixture was raised to 100 C. and 216 parts of isopropanol was distilled ofi and a polymeric titanium butyrate produced which had a few isopropoxy groups (less than /2 mole unit isopropoxy radical per atom of Ti) still remaining attached to the Ti atom. To this polymeric titanium butyrate was added 565 parts of oleic acid with agitation and 186 parts of distillate was then distilled off, of which 164 parts was butyric acid. The reaction product was found to consist essentially of polymeric titanium oleate.
Example 11 (CH3)2CHCOO -TlO- OCCIHCHDB OZCixHss it was obtained by distilling off the resultant 2 mole parts of isobutyric acid.
While the invention has been described as applied to certain specific embodiments thereof, it is not restricted thereto. Hence, due variance therefrom can be resorted to without departing from its underlying principles and scope. Thus, the polymeric or condensed titanium or zirconium acylate useful as a starting reactant herein has substantially the general formula:
wherein Y and Y in the chain terminating groups comprise an alkyl (methyl, ethyl, propyl, butyl, etc.) or an acyl radical, R and R equal a radical selected from the group hydrogen, alkyl, cycloalkyl, aryl radical, alkene or an alkylaryl radical, and x is greater than 1 and preferably ranges from 2-100. Pr ferably the acylate O O (O&R) and (O i JR) substituent groups are such that in the reaction the exchanged acid evolved or produced therefrom is of relatively low boiling point, e. g., will contain from 2-5 carbon atoms and not more than 8 carbon atoms in its chain. Among examples of preferred useful polymeric acylates, polymeric titanium or zirconium acetate, polymeric titani um or zirconium propionate, polymeric titanium or zirconium isobutyrate, and the like, can be mentioned. The polymeric or condensed titanium acylates are especially useful and preferred for employment. They can be readily prepared by reacting an alkyl orthotitanate, such as tetraethyl titanate, with a carboxylic acid and a regulated quantity of water, as contemplated in my U. S. Patent 2,621,195. Thus, as disclosed in that patent, to one mole of an ortho ester of titanium there can be added about two moles of a monocarboxylic acid and controlled addition then effected of about one mole water per atom of titanium, followed by heating of the reactants until the desired polymeric polytitanic ester is formed. Alternatively, the methods disclosed in U. S. Patent 2,621,193 can be utilized in effecting such preparation. The product of such reactions, depending on the exact quantities of reactants, will contain a small amount of residual alkoXy radical, in the terminal group for example, not completely removed by the acylation reaction. Furthermore, by reacting the proper quantity of carboxylic acid with the titanium acylate, a mixed titanium acylate hav- 4 ing any desired ratio of acylate groups may be produced. Such mixed titanium acylates can be produced by reacting less than the stoichiometric equivalent of carboxylic acid with the titanium acylate and separating the co-product carboxylic acid from the reaction mixture. Such a a reaction is represented by the equation:
point than the exchangeable acyl radical of the original titanium or zirconium acylate in the acid form. For example, in the case where the original compound is polymeric titanium butyrate, the polymer unit being represented by the formula any carboxylic acid boiling higher than n-butyric acid can be used. Examples of such acids include those containing decanoic, hyptylic, sabacic, caprylic, capric, palmitic, oleic, stearic, lauric, behenic, adipic, benzoic, ortho chlorbenzoic, trichloroacetic, etc. Mixtures of acids, such as, for example, those occurring in natural fats and oils, and the like, are also contemplated for use. A wider choice, with regard to boiling point of reactant carboxylic acids, can be used when the co-product carboxylic acid is separated from the product titanium acylate by means other than distillation, as for example fractional crystallization or precipitation of either the coproduct carboxylic acid or the product polymeric titanium acylate.
While specific temperatures have been mentioned and utilized herein, the invention is not to be construed as restricted thereto. In general, use is contemplated of any temperature designed to control and effect the desired reaction and the subsequent recovery, by distillation, of the acylating acid which is displaced. If desired, recourse can be had to any convenient and desired pressure during the distillation.
I claim as my invention:
1. A process for acidolysis of a polymeric group IV metal acylate corresponding to the formula wherein Y and Y are selected from the group consisting of an alkyl and acyl radical, R and R are selected from the group consisting of hydrogen, alkyl, cycloalkyl, aryl, alkene and alkylaryl, and x is a number greater than 1, with a carboxylic acid having a higher boiling point than the carboxylic acid co-product which corresponds to the acyl radical of said polymeric metal acylate reactant, removing by distillation from the reaction mass co-product carboxylic acid formed in the reaction, and recovering the resulting polymeric group IV metal acylate product.
3. A process for producing a polymeric titanium acylate comprising reacting about one mole unit of a polymeric titanium acylate corresponding to the formula:
wherein R and R are selected from the group consist ing of an alkyl, cycloalkyl, aryl, alkene and alkylaryl radical, and x is a number greater than 1 with about two moles of a saturated, monocarbcxylic acid having a higher boiling point than the carboxylic acid product of an acyl radical in said acylate reactant, removing by distillation co-product acid formed in the reaction, and recovering the desired polymeric titanium acylate reaction product.
4. A process for the production of polymeric titanium stearate, by commingling and reacting in a reaction vessel about two moles parts of stearic acid with one mole part of polymeric titanium butyrate, removing by distillation co-product butyric acid formed in the reaction and recovering the resulting acylate product.
5. A process for the production of polymeric titanium oleate, by commingling and reacting in a reaction vessel about two moles parts of oleic acid with one mole party of polymeric titanium butyrate, removing by distillation co-product butyric acid formed in the reaction and recovering the resulting acylate product.
6. A process for the production of polymeric titanium oleate, by commingling and reacting in a reaction vessel about two moles parts of oleic acid with one mole part of polymeric titanium propionate, removing by distillation co-product propionic acid formed in the reaction and recovering the resulting acylate product.
7. A process for producing polymeric mixed titanium acylates comprising commingling and reacting a polymeric titanium acylate corresponding to the formula:
References Cited in the file of this patent UNITED STATES PATENTS Boyd Oct. 14, 1952 2,621,194 Balthis Dec. 9, 1952 2,621,195 Haslam Dec. 9, 1952
Claims (1)
1. A PROCESS FOR ACIDOLYSIS OF A POLYMERIC GROUP IV METAL ACYLATE CORRESPONDING TO THE FORMULA
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| US337438A US2708203A (en) | 1953-02-17 | 1953-02-17 | Preparation of polymeric titanium organic compounds |
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| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| US337438A US2708203A (en) | 1953-02-17 | 1953-02-17 | Preparation of polymeric titanium organic compounds |
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| US2708203A true US2708203A (en) | 1955-05-10 |
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| US337438A Expired - Lifetime US2708203A (en) | 1953-02-17 | 1953-02-17 | Preparation of polymeric titanium organic compounds |
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Cited By (8)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US2916392A (en) * | 1958-04-07 | 1959-12-08 | Monsanto Chemicals | Air drying films from unsaturated fatty acid metal salts |
| US2985604A (en) * | 1957-03-05 | 1961-05-23 | Union Carbide Corp | Shaped resins |
| US2985607A (en) * | 1957-03-05 | 1961-05-23 | Union Carbide Corp | Rubber additives |
| US2989412A (en) * | 1956-04-17 | 1961-06-20 | Union Carbide Corp | Organometallic pigment dispersants based on acylates polyhydric alcoholates and aminoalcoholates of group iv-b metals |
| US3098041A (en) * | 1961-11-20 | 1963-07-16 | Union Carbide Corp | Lubricating composition |
| US3180741A (en) * | 1960-11-29 | 1965-04-27 | Horizons Inc | Liquid polymers, solid articles made therefrom and methods of preparing same |
| US3243447A (en) * | 1960-10-31 | 1966-03-29 | Rinse Jacobus | Preparation of spacial tetrameric acyloxy group iv metal oxides |
| EP0625564A1 (en) * | 1993-05-18 | 1994-11-23 | INDIAN OIL CORPORATION Ltd. | Lubricating oil |
Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US2614112A (en) * | 1951-01-30 | 1952-10-14 | Monsanto Chemicals | Polymeric titanium mixed esters |
| US2621195A (en) * | 1950-10-26 | 1952-12-09 | Du Pont | Polymeric titanium compounds |
| US2621194A (en) * | 1950-07-26 | 1952-12-09 | Du Pont | Polymeric hydroxyl-containing titanium carboxylates and methods for preparing same |
-
1953
- 1953-02-17 US US337438A patent/US2708203A/en not_active Expired - Lifetime
Patent Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US2621194A (en) * | 1950-07-26 | 1952-12-09 | Du Pont | Polymeric hydroxyl-containing titanium carboxylates and methods for preparing same |
| US2621195A (en) * | 1950-10-26 | 1952-12-09 | Du Pont | Polymeric titanium compounds |
| US2614112A (en) * | 1951-01-30 | 1952-10-14 | Monsanto Chemicals | Polymeric titanium mixed esters |
Cited By (8)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US2989412A (en) * | 1956-04-17 | 1961-06-20 | Union Carbide Corp | Organometallic pigment dispersants based on acylates polyhydric alcoholates and aminoalcoholates of group iv-b metals |
| US2985604A (en) * | 1957-03-05 | 1961-05-23 | Union Carbide Corp | Shaped resins |
| US2985607A (en) * | 1957-03-05 | 1961-05-23 | Union Carbide Corp | Rubber additives |
| US2916392A (en) * | 1958-04-07 | 1959-12-08 | Monsanto Chemicals | Air drying films from unsaturated fatty acid metal salts |
| US3243447A (en) * | 1960-10-31 | 1966-03-29 | Rinse Jacobus | Preparation of spacial tetrameric acyloxy group iv metal oxides |
| US3180741A (en) * | 1960-11-29 | 1965-04-27 | Horizons Inc | Liquid polymers, solid articles made therefrom and methods of preparing same |
| US3098041A (en) * | 1961-11-20 | 1963-07-16 | Union Carbide Corp | Lubricating composition |
| EP0625564A1 (en) * | 1993-05-18 | 1994-11-23 | INDIAN OIL CORPORATION Ltd. | Lubricating oil |
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